JPS6215384A - Fluoropolymer composition and its production and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to fluorine-containing polymer compositions that impart durable oil and water repellency to Il fibrous matrices. The present invention also includes: It also relates to a method of treating the substrate to impart durable oil and water repellency. The invention further relates to said fibrous substrate treated with the composition of the invention. In addition, the present invention relates to a method for producing the composition of the present invention.

BACKGROUND OF THE INVENTION Polymers and other compounds containing highly fluorinated segments are widely used to impart oil and water repellency to textile substrates. for example.

FaSik et al., in U.S. Pat. No. 3,378,609, disclose at least 11 polyfluoroalkyl acrylates or methacrylates, at least one alkyl acrylate and methacrylate, dialkylaminoethyl acrylate and methacrylate, and methylol acrylamide and methylol methacrylamide. A composition containing a copolymer derived from a non-vinyl fluorine-free polymerizable vinyl compound, such as, is disclosed.

Also.

At least one non-vinyl fluorine-free or non-fluorinated conjugated diene, such as 2-chloro-1,3-butadiene or 2,3-dichloro-1,3-butadiene
Compositions containing a mixture of a vinyl polymer derived from a species of polymerizable compound and one of the aforementioned polymers are disclosed.

US Pat. No. 3,923,715 to Dettre et al. states that the preferred compound is tris(2-perfluoroalkylethyl)citrate urethane. Provides other examples. In one example, Dettre et al. add a non-fluorinated vinyl polymer, such as polymethyl methacrylate, to an aqueous dispersion of a perfluoroalkyl ester mixture. Reynolds and Read, U.S. Pat.
No. 491,169 discloses copolymers derived from mixtures of polyfluoroalkyl methacrylate, lauryl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate, and methylolacrylamide or methylolmethacrylamide. The latter two monomers are added in amounts up to 0.5% by weight and serve to suppress the shedding of the copolymer during laundering or dry cleaning of the fabrics to which it has been applied. In U.S. Pat. No. 3,462,296.

RaVnolds and Tandy are Raynold
discloses a copolymer that is similar to the copolymers of S and Read, but differs in that 2-ethylhexyl methacrylate is used in place of lauryl methacrylate in the relative amounts of the components of the copolymer.

Prior art polymers are generally used for emulsion stabilization.
Produced by emulsion polymerization using either anionic or cationic surfactants.

The surfactant content of the dispersion or latex.

This often prevents effective deposition of polymeratex particles on the textile substrate that treatment is desired. Thus, when the 1wt substrate comes into contact with an aqueous composition containing latex, a cationic surfactant, etc., some of the cationic surfactant migrates to the textile substrate.

deposited on top of it, making the substrate cationic and thus #
A. Prevents effective deposition of cationic polymeratex particles on animal substrates. Similar problems, but for different reasons, arise when polymalatexes are made using anionic surfactants. All materials used in textile fiber production develop a negative charge when they come into contact with water. Polymeratex or dispersed particles containing anionic surfactants will then be repelled by such IIMs. above.

observed in latex containing cationic and anionic surfactants. The effect on the deposition of latex particles on the textile substrate is hereinafter referred to as the "disturbance effect". Nonionic surfactants cannot be used in the emulsion polymerization method in question. This is because at temperatures high enough to cause a significant portion of the nonionic surfactant to dissolve into the organic phase, the nonionic surfactant will flow and cause coagulation of the latex. At such temperatures, the cationic and anionic surfactants remain in the aqueous phase and the latex does not coagulate.

[Summary of the Invention] According to the present invention, 1) the use of the composition of the present invention produced by the method of production of the present invention, the "interfering effect" is minimized. The composition was prepared in the presence of a nonionic surfactant and an anionic surfactant in combination with an amphoteric polymer. Includes one or more polymeratex or fluorocarbon dispersions. Optionally, the compositions of the present invention may include anionic elastomalatex. According to the method of the invention, a nonionic surfactant is mixed with the anionic surfactant-containing polymer and/or fluorocarbon dispersion and elastomalatex prior to the addition of the monoampholytic polymer.

[Detailed Description of the Invention] Polymer 1atex or
1atxes) may be used for any polyfluoroalkyl-containing polymer, provided that the polymer is prepared by emulsion polymerization using an anionic surfactant or an anionic surfactant is used in the preparation of the fluorocarbon dispersion. It may be a polymeratex or fluorocarbon dispersion. Examples of such fluorocarbons and polymers are the fluorocarbons disclosed in the above-mentioned patents;
polymers and polymer mixtures, the contents of which patents are incorporated herein by reference. The nonionic surfactant is H
Compounds with LB of 15±3 include oxyethylated or oxypropylated alcohols, phenols, polyols, amines, etc., and one example is given in the literature (McCutcheon
's Emulsifiers & Dete
raents, 1984゜North Al11
Erican Edition, pages 299
-308).

For the purposes of the present invention, an amphoteric polymer is used as a result of its addition to the dispersion and as a result of adjustment of the pH to a pH that is slightly more acidic than the pH that is the isoelectric point of the dispersion. , is defined as a compound that renders a latex or dispersion with anionic zeta potential cationic. Typically, a change in IpH units2, e.g.
A change from pH 7 to pH 6 is sufficient. The zeta potential ranges from 1 strongly anionic to 0 mildly ionic 9
For example, a sufficient amount of amphoteric polymer is used to adjust the pH value from +15 to +30 millivolts. Usually, an addition of 1 to 50% by weight of amphoteric polymer, based on the solids weight of the anionic dispersion or latex, is sufficient. Typical examples of amphoteric polymers are dialkylaminoalkyl acrylates, with or without fluoroacrylates or fluoromethacrylates, with or without acrylic or methacrylic acids, with or without alkyl acrylates and/or methacrylates. Or a copolymer of methacrylate. As well as 3-chloro-2-hydroxypropyl acrylate or methacrylate.

Glycidyl acrylate or methacrylate can be used in such copolymers. The dialkylaminoalkyl acrylate or methacrylate can be used in its form or I! It can be used in the form of salt, N-oxide and betaine.

According to the production method of the present invention, the nonionic surfactant is
It is essential that the amphoteric polymer be combined with all anionic components of the composition prior to the addition of the amphoteric polymer. When a 2-ampholyte polymer is added to the anionic component of the composition without the presence of an effective amount of a nonionic surfactant, the 1-ampholyte polymer causes a change in the zeta potential from negative to positive;
Coagulation of the latex or dispersion will occur. Thus, all components of the composition other than the amphoteric polymer can be blended in any order as long as the nonionic surfactant is blended with all anionic components prior to addition of the amphoteric polymer. can. In a preferred embodiment, the composition of the present invention is used in blank decorative material fabrics.

It is especially used to impart oil and water repellency to polypropylene fibers. In that embodiment, an abrasion resistant material such as polychloroprene is used in the form of an anionic latex.

Methods using the compositions of the present invention impart oil and water repellency to 1111!1 substrates by applying an effective amount of the compositions of the present invention to a substrate. In that way.

First, one or more fluorocarbon dispersions and/or polyfluoroalkyl-containing polymeratexes containing anionic surfactants.

Blend with a nonionic surfactant having an HLB of 15±3. Sufficient amphoteric polymer is then added to render composition 9 slightly cationic to facilitate deposition of composition 2 onto the substrate.

A specific example of a composition particularly suitable for imparting oil and water repellency to nylon, polyolefin, and acrylic upholstery fabrics is a mixture of two different anionic fluorocarbon dispersions and/or polymalatexes:
Used with anionic polychloroprene latex. Compositions of this type are illustrated in the examples herein.

Zeta Potential The zeta potential of an aqueous latex or dispersion is
Measured with a zetameter. The velocity of colloidal particle movement in an electric field is measured by direct observation using a stereomicroscope and reflected beam illumination. Water droplets are 0 references (Zet
a-Meter Manual.

2nd edition, Zeta-Meter, Inc.
New York) and is suitable for particles larger than about 0j-0.2 microns in diameter. Since many of the product baths being studied in this invention contain particles smaller than 0.1 micron, the zeta potential determined from tracking of relatively large particles.

It is assumed to be representative of the entire size range of particles in the bath.

To eliminate the effects of temperature changes that affect the movement of particles in the zetameter cell, the nine particles were tracked in one direction by reversing the polarity of the cell. At least 100 particles were tracked for each zeta potential determination.

Oil repellency test (AATCC test 118) A piece of fabric treated with an aqueous dispersion of the polymer of the invention was tested at 23±2°,
The apparatus was kept under conditions of relative humidity 65±10% for at least two hours. Oil and water repellency of carpet samples should be measured on the sides of the yarn, not on the tips of the tassels. Starting with the lowest grade test liquid (first class oil and water repellency evaluation), one drop (approx.
IIl or a volume of 0.05 m1 at least 5 m
It was placed at each of three points separated by l. The droplet was observed for 30 seconds.

At the end of the observation period, if 2 of the 3 drops are still spherical or hemispherical in shape and no wicking is observed around the droplets, add 3 drops of the next higher grade test solution next to them. position and observed again for 30 seconds. 2 out of 3 drops of a certain test solution are 1
This procedure was continued until no spherical or hemispherical shape was maintained or wetting or wicking occurred. The oil repellency evaluation of the yarn or fiber was such that 2 out of 3 drops remained spherical or hemispherical and no wicking was observed for 30 seconds. This is the highest grade test liquid.

Standard oil test liquid oil repellency evaluation series Composition 1 "Nujol" * 2 65/35 Volume ratio of "r Nujol"/n-hexadecane 211 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane * [Nujol ( NLIjOl) J is Saybolt viscosity at 38° 360/390, specific gravity at 15° 0.88
010.900 against mineral oil. Trademark (Plow
, Inc.).

A piece of fabric treated with the aqueous dispersion or latex of the composition of the present invention was kept in the apparatus for at least 2 hours at 21±1° C. and 65±2% relative humidity. The textile test sample was placed so that the surface to be tested was flat and horizontal. Start with the lowest grade test liquid (water repellency rating 1st class) and add 1 drop (approximately 5 mm in diameter).
in or a volume of 0.05i1 at least 5cm
I placed them at each of three separate points. Care must be taken not to place the test liquid in the same position used for the oil repellency evaluation.

After 10 seconds, if 2 of the 3 drops still appear to be spherical or hemispherical, place 3 drops of the next higher grade test solution adjacently and observe for 10 seconds. 2 out of 3 drops of a certain test solution are 0
Continue this process until it no longer holds a spherical or hemispherical shape. Water repellency evaluation of woven yarn.

Two out of three drops remained spherical or hemispherical for at least 10 seconds. This is the highest grade test liquid.

Star! ” Gen 1 Ri IR Water repellency Composition Flash point (TCC) evaluation series % Isopro % Distillation ℃°F Panol * H2
O 2595F/'o 122 * For reagents, volume percent, manufactured by Merck
, I nc, , Rahway, N.J.
).

i The abrasion resistance of upholstery fabrics has been described elsewhere (
AA-CCTe5t Method 8-1981
>Measured by the dry-locking test method.

Typical Preparation of Components for Preferred Embodiments The following examples are illustrative of the present invention. Unless otherwise indicated, all parts and percentages are by weight and temperatures are in degrees Celsius. In the description of the polymers produced below,
The percentages of monomer units shown for the polymers are based on the weight of monomer charged to the two reactions.

A tris(2-perfluoroalkylethyl) citrate mixture was produced using a 2-perfluoroalkyl ethanol mixture in No. 11. A mixture of 2-perfluoroalkylethanols is a mixture of 2-perfluoroalkyl ethanols whose perfluoroalkyl groups CF30F2
In (CF2)k.

k is 2, 4, 6, 8, 10.12 or 1
It's 4.

The approximate heavy-duty ratio is 1/33/3L/18/ 8/ 3/
1, and this mixture has an average molecular weight of about 452. 2-Perfluoroalkylethanol (4
306 klJ) at 70 ± 5°, anhydrous citric acid (5
62 kl; 1) was blended with stirring. after that.

Granular boric acid (2.7 kg) and aqueous phosphorous acid (6.4 kQ of a 70% solution) were added as catalysts. Increase the temperature of the reaction mixture for 3-4 hours or more with stirring.

The angle was raised to 130±5°. While removing the water generated from the reaction of 2-perfluoroalkylethanol and citric acid, W&
Stirring was continued for 23-24 hours. When analysis indicated completion of esterification, 1 the reaction temperature was lowered to 70-80° and butyltin trichloride (5.9 ko) was added. The temperature was adjusted to 70-75° and hexamethylene diisocyanate (255 kg) was added. The concentration was increased to 80-86° and held at that temperature for approximately 6 hours. Then increase the temperature to 92±2
The reaction mixture was stirred at that temperature for 8 hours. Then the reaction temperature was lowered to 55-15° and methyl isobutyl ketone (2312 kG) was added. Reaction temperature to 60
The temperature was adjusted to -70° and the mixture was stirred for 1-2 hours. The product is a solution of tris(2-perfluoroalkylethyl) citrate urethane weighing 7003 kO in methyl isobutyl ketone, containing 4392 kO of tris(2-perfluoroalkylethyl) citrate urethane mixture.

Methyl isobutyl ketone (419
tris(2-perfluoroalkylethyl)citrate urethane mixture (851k) dissolved in
O) in WA ionized water (1419klJ) and aqueous sodium dodecylbenzenesulfonate (85k of a 30% solution).
Emulsified with (1). Methyl isobutyl ketone was then removed from the emulsion by vacuum distillation. The resulting dispersion was standardized to 40±1.5% citrate urethane using deionized water.

The fluoromonomer mixture used in this method has the following formula:

CFsCFt (CF2)kCHtCHtOC(0)
C(CHs)-CHz where k has the same value and distribution as described above and the average molecular weight of the fluoromonomer mixture is 520.

Deionized water (515k(1) to aqueous sodium dodecylbenzenesulfonate (210kQ of 30% slurry)
It was mixed while stirring. Stir at 45±5° for 10-1
It lasted for 5 minutes. The above mixture of fluoromonomers (816
kill) with 2-ethylhexyl methacrylate (272 kg) in a separate container and stirred for 10 minutes at 45 ± 5°, then the fluoromonomer mixture and 2-ethylhexyl methacrylate (2-EHMA) was added to a mixture of deionized water and sodium dodecylbenzenesulfonate. Homogenized generation charges. The homogenizer was rinsed with deionized water (363 kg) and the rinse water was added to the homogenized emulsion. In a separate container, primary dodecyl mercaptan (545Q), hydroxyethyl methacrylate (2,7 ka, 94% llIi degree), and aqueous N-methylolacrylamide (5,7
kQ) was mixed at room temperature and then blended with the above homogenized emulsion with stirring for 5-10 minutes. Then, combine the generated charge with deionized water (1451 kg)',
The charge was stirred at 65±2° for at least 30 minutes. Then add azobisisobutyramidine (436Q'') dissolved in deionized water (2-3 quarts).

The polymerization of the charge was allowed to proceed with stirring for 4 hours at a temperature maintained at 70±2°. Then charge 30-35
The weight of the final product is 3606 k (J), of which 1021 k (J constitutes the polymer).

Latex II The fluoromonomer mixture used in this production was:

Essentially identical to that of Latex I.

Deionized water (333 kq) was mixed with aqueous sodium lauryl sulfate (37 kg of a 30% solution) with stirring at 50-55°.
6±0.5 ko). In a separate vessel, the fluoromonomer mixture (358±3 klj) was combined with lauryl methacrylate (193±1.8 ka) and the resulting charge was stirred for 5-10 minutes to mix well. after that,
The blended monomers were stirred and mixed with sodium lauryl sulfate, and then homogenized. After homogenization.

The equipment used for homogenization was rinsed with demineralized water (182 ka) and the rinse water was added to the homogenized dispersion. after that.

Lauryl mercaptan (891±h) and N-methylolacrylamide (2,31±o, 05ko) were added to the homogenized dispersion of monomers. Generation charge 80-85°
Added to deionized water (737k(+) at 65±
The temperature was adjusted to 1° and stirring of the charge was continued for 30 minutes. N,
N'-Azobisisobutyramidine dihydrochloride (218±2a) was dissolved in approximately one gallon of water. 70
Polymerization was allowed to proceed with stirring at ±1° and maintained at that temperature for 4 hours. The resulting polymer product was cooled to 30-40' and enough deionized water (approximately 547 ka) was added to give a solids content of 22.5%.

Polymer I In contrast to the emulsion polymerization method described above, Polymer I was prepared by solution polymerization.

Deionized water (615 kG) and 2-dimethylamine ethyl methacrylate (250 kG) were blended at 20° with stirring. Wood vinegar! fl (95 ka) was added to the mixture, stirred for 10-15 minutes, and acrylic acid (57 ka) was added to the mixture.
) was added. Charge the above charge with deionized water (461k
a) and isopropyl alcohol (461 ha) for 15-20 minutes. Adjust the charge temperature to 65±2° and i! Stirring was continued for 30 minutes.

At that point, 2 dissolved in deionized water (3,8k(1)
゜2'-Azobisisobutyramidine dihydrochloride (409 kg>) was added. Polymerization was allowed to proceed with stirring at 70 ± 2° for 18 hours. At a charging temperature of 10°,
Add deionized water (30 times to one polymerization charge for 5 minutes)
923 kg) was added.

-Tex III Commercially available chlorobrene and 2,3-dichloro-1,3-butadiene (DUPontNeo
A copolymer of prene Latex 400) was used. This latex contains 50 wt-% solids and has a specific gravity of 1.15 at 25°D H12,5, 25°
．． Average particle size 0.12 microns, surface tension 37.1 dynes/cm.

and a Brookfield viscosity of 9 cp. The commercially available latex was diluted with deionized water to a solids content of 6% and it was neutralized to pH 6.3 with 10% acetic acid.

L Dispersion 1 (575 parts), Latex 1 (576 parts).

and Latex II (400 parts) were mixed with slow stirring at room temperature, and aqueous ethoxylated sorbitan monooleate containing 20 ethylene oxide units (580 parts of a 20% solution, Tween 80) was added with stirring. Latex III was added with stirring over 1-1.5 hours, then Polymer I was added with stirring over an additional 1-1.5 hours. The resulting mixture was neutralized with triethanolamine to pH 6,5-6,9.

Final blend contains 2.15%. Zeta potential measurements were performed on aqueous product dilutions, yielding zeta potentials between +20 and +28 millivolts.

Polypropylene fabrics were treated with the final product blend by pad application such that the blend was 2% based on fabric weight. It was rated 8th grade in the oil repellency test, and 5th grade in the water repellency test. cotton friction 10
After cycling, oil repellency was 2-3 grade.

Example 2 was repeated replacing L Polymer I with a solution polymer (900 parts) of 75 parts of butyl methacrylate and 25 parts of diethylaminoethyl methacrylate N-oxide. The resulting latex product was applied to polypropylene fabric by spray application at a level of 2% latex based on part #11 and obtained an oil repellency rating of 5+ and a water repellency rating of 4@.

Polymer I was replaced with a solution polymer (900 parts) of dimethylamine ethyl methacrylate/methyl methacrylate/acrylic acid in a molar ratio of 2/1/1.

Example I was repeated. The resulting latex was applied to polypropylene fabrics by spray application at a level of 2% and obtained an oil repellency rating of 6th grade and a water repellency rating of 4th grade.

L Polymer I in a molar ratio of 2. /1/1 diethylaminoethyl methacrylate/methyl methacrylate/acrylic acid solution polymer (1220 parts).

Example I was repeated. When applied to polypropylene fabrics at a level of 2%, an oil repellency rating of 5+ and a water repellency rating of 4 were obtained.

Example 2 was repeated by replacing Polymer I with a solution polymer (1220 parts) of dimethylaminoethyl methacrylate/methyl methacrylate/acrylic acid/butyl acrylate in a molar ratio of 1.9/1/110.1.

Applied to polypropylene fabric by spray application at a level of 2% based on fabric weight.

It received a 6th grade oil repellency evaluation and a 5th grade water repellency evaluation.

1. Polymer I was mixed with 75 parts of 2-ethylhexyl methacrylate and 25 parts of diethylaminoethyl methacrylate N-
Example 2 was repeated, substituting the oxide solution polymer (900 parts). It was applied to polypropylene fabrics by spray application at a level of 2% based on the weight of the fabric and obtained an oil repellency rating of 50th 1m and a water repellency rating of 4th grade.

=W Polymer I with 85 parts of 2-methyl methacrylate and 15
Example 9 was repeated, substituting 1035 parts of diethylaminoethyl methacrylate acetate solution polymer. It was applied to polypropylene fabrics by spray application at a level of 2% and obtained an oil repellency rating of 4th grade and a water repellency rating of 5NL.

Polymer I, 90 parts of butyl methacrylate, 8 parts of dimethylaminoethyl methacrylate, and 2If
Solution polymer containing f1 part of acrylic acid (900 parts)
Example 1 was repeated in place of . It was applied to polypropylene fabrics with 9 spray applications at a level of 2% based on the weight of the fabric and obtained a la oiliness rating of 1iIli 5th grade and a water repellency rating of 5th grade.

Similar results were obtained by repeating the procedure of the above example, substituting the following solution amphoteric polymers for L1Ny Polymer I. Fluoromonomer (FM
) The mixture is essentially that of Example 2.

Ward "L" L Engineering - Monomer 29, MMA/DEAM/AMPS 30, Butyl methacrylate/DEAM Acetate 3
1, FM/DEAM・Acetate 32, MMA/DEAM・(CH3) 2 SO4 4th
Class 33, MMA/CHPM/DEAM・(CH3) 28
04 4th grade 34, RI CH2CH25CH2CH2Coo (
-) NH4(+) (Rf - essentially the same CF2 distribution as FM) 35, DEA
M/Hydroxyethyl methacrylate/AA38.2-
EHMA/MMA/DEAM-N→037.2-EHM
A/MMA/DEAM-N→038, CHPM/DEA
MN→0 39, DMAM/MMA/β-carboxyethyl acrylate 1”LC] and L +O/L da/Jr 37, 5/37.5/25

Claims (4)

[Claims] (1) After blending one or more fluorocarbon dispersions or polyfluoroalkyl-containing polymalatex containing anionic surfactant with a nonionic surfactant having an HLB of 15±3, the composition is The composition was prepared by rendering it cationic and blending it with an amphoteric polymer in an amount sufficient to facilitate deposition of the composition onto the substrate. A method of imparting oil and water repellency to a fibrous substrate comprising applying an effective amount of a composition. (2) The fiber substrate is polypropylene. A method according to claim 1. (3) The method of claim 2, wherein the polypropylene fabric is an upholstery fabric. (4) Producing the composition by blending the polyfluoroalkyl-containing latex or dispersion with the nonionic surfactant- and anionic surfactant-containing elastomalatex prior to addition of the amphoteric polymer. The method according to claim 3, wherein: